Heavy duty lubricating oil



United States Patent- V The present invention is directed to-an: improved lubri- .cating Y oil. -More particularly, the present invention; is

directed to a lubricating -oi1.composition: suitableior use under heavy duty conditions. In its more specific .aspects,

the invention is directed to a useful lubricatingbilrhaving improved stability characteristics.

The present inventionnmaybe-briefly described .as a

lubricating oil composition ofimproved stability which comprises synergistic amounts: of an orthoalkylated phenol and an alkaline earth metal sulfonate in admixture with a lubricating oil 'frac'tion.

The lubricatingoil fraction-employedin the practice of the present invention may suitably be a paraffinic or naphthenic type-lubricating oily such as produc'ed from "Gulf Coastal; Panhandle, and Pennsylvaniafand' Galifornia type crude-oil. Thelubricating oil fraction'may suitably have a range'inviscosity-from about 3510' about 160 Saybolt Seconds Universal at"210 "F. Whiletlie lubricating oil fraction is preferably a'petroleun'i lubricating "oil fraction; other lubricating 'oils'may be employed in the composition of thepresent invention. Thus, lubricating oils produced syntheticallyby polymerizing olefins to oils of the'proper molecular weight and having Llubri- 'cating' oil"characteristicsidthe viscosity range indicated may be used.

The amount of the composition made up of the lubricating oil fractions will suitably be in the range from about 93 percent to about 98 percent by Weight of the composition.

The composition contains synergistic amounts of an orthoalkylated phenol and an alkaline earth metal sulfonate. The orthoalkylated phenol is suitably an orthoalkylated phenol such as 2,6 di-tertiary butyl phenol, 2,6 di-tertiary-a-dimethylamine para-cresol, 4,4-methylenebis (2,6-di-tertiary butyl phenol), ortho-tertiary butyl phenol, and 2,4,6 tri-tertiary butyl phenol.

The amount of the orthoalkylated phenol employed suitably ranges between about 0.5 percent and about 2 percent by weight of the composition.

The alkaline earth metal sulfonate may be any of three alkaline earth metal sulfonates, such as calcium, barium, or strontium, but preferably is calcium or barium sulfonate. These alkaline earth sulfonates may be suitably formed by alkylating benzene with tetrapropylene to form a long chain alkylated aromatic hydrocarbon, followed by sulfonation of the alkylated hydrocarbon, and then neutralizing the sulfonated alkylated aromatic hydro carbon with barium or calcium hydroxide or oxide. Other means for preparing the sulfonate may be employed, for example, by photosulfochlorination of saturated hydrocarbons with corresponding treatment of the sulfonyl chloride with barium or calcium oxide or hydroxide.

The synergistic amount of the alkaline earth sulfonate is between about 1 percent and about 5 percent by weight of the composition.

The alkaline earth sulfonate may contain a co-neutralized alkyl phenate in admixture with the alkaline .12 e'a'ith'.-metalsulfonate. When a co-neutfalized--.alky1 Q phenat .is employed; it should be, employed withlthe 4 l-alkaline earth metal sulfonate in a ratioof twoparts'iof the alkaline ,earth metal s'ulfonate to about 1. partfoflthe col-neutralized'alkyl phenate.

f As examples of the Yalkyl'phenates may be mentioned .tnonyl' barium 'phenate, sulfurized nonyl. barium phenate, sulfurized calcium-barium nonyl phenate, alndiilfiiriitid calcium nonylf'phenate. I In. o'rder to illust'rate the-present invention. further a -"nuhiber. of compositions were made .up in accordance with. the present invention inwhich synergisticamounts oft-he orthoalkylated phenol and the alkaline earthinetal siilfonate were employed." These compositions'were-com- .par.ed with 5 other. compositions employingl ".the. ortho- I alkylated phenol and. the; alkaline earth metal animate j alonef Further comparisons were made withscomposh :tio'ns of'theprior art.

The sevei'al blends were subjected to amodified Indiana 20. Life -test..for 32 :hoursandthe percentincreasejn viswcbsity (Saybol't Seconds Universal) at. 1 00.- Frwas estab- Jlish'ed by determining the viscosity every 8 hours-and j -plotting' percent viscosityincrease versus' time.- -Identity of. the several blends and theresults. of theIndianaI-ife t'es't arepresent'edin the. following table: 1

I Table I regce it Vis- 0051? name Additive (Aften32Hours in Mddified lndianahite '..Test) 1 Based-0 75 Wt. Percent 4,4 Methylenebis' (2,6-d1-tert-hutyl phenol).

=Base '1.5"- Wt." Percent 4,4Metl1ylenebis (2,6di-tert'butyl phenol).

Base+0.5 Wt. Percent 2,6-di-tert-butyl-adimethyIamine-p-cresol.

Base+1.0 Wt. Percent 2,6-dbtert-butyl-adlmethylamine-p-cresol.

Base+1.5 Wt. Percent 2,6-di-tert-butyl-adimethylamine-p-cresol.

Base+2.5% suliurized nonyl barium phenate.

Base+5.0% 1 part calcium sulfonate, 2 parts co-neutralized Sulfurlzed nonyl calciumbarium phenate.

Base+2.5% 2 parts barium sulfonate, 1 part tic-neutralized sulfurized nonyl calciumbarium phenate.

Base+4.0% Ca Sulfonate Base+2.5% Ba Sulfonate Based-2.5% sulfurized nonyl barium phenate, 1.0% 44 Methylenebis (2,6-di-tertbutyl phenol) (Wt.).

Based-5.0% 1 part calcium sulfonate, 2 parts co-neutrahzed sulfunzed nonyl calciumbaiium phenate; 1.0% 4,4 Methylenebis (2,6-di-tert-butyl phenol) (Wt).

Basel-5.0% 1 part calcium sulfonate, 2 parts ctr-neutralized sulfurized nonyl calciumbarium pheuate; 1.0% 2,6-dl-tert-butyllX-dl-IIlGlGlJYlSDJiHG-P-CTGSOl (Wt).

Base+2.5% 2 parts barium sulfonate, 1 part (to-neutralized suliun'zed nonyl calciumbarlum phenate; 1.0% 4,4 Mcthylenebis (2,6-di-tert-butyl phenol) (Wt.).

Base+2.5% 2 parts barium sulfonate, 1 part (ac-neutralized sulfun'zed nonyl calcium barium phenate; 1.0% 2,6di-tert-butyl-adi-methylamme-p-cresol (Wt).

Base+4.0% Ca Sulfonate, 1.0% 4,4 Methylenebis (2 fi-di-tert-butyl phenol) (Wt.).

Base+2.5% lBa Sulfonate, 1.0% 4.4 Methylenebis (2,6'di-tert-butyl phenol) (Wt.).

Base+2.5% 2 parts barium sulfonate, 1 part tic-neutralized sulturized nonyl calciumbarium phenate; 0.75% 4,4 Methylenebis (2,6-dl-tert-butyl phenol) (Wt.).

Basel-2.5% 2 parts barium sulfonate, 1 part co-neutralized sulfurized nonyl calciumbarium phenate; 0.5% 4,4 Methylenebis (2,6 dl-tert-butyl phenol) (Wt.).

From the data presented in the preceding table, it will be clear that the blends containing both the alkaline earth Patented Sept. 27, 1960 metal sulfonate and the orthoalkylated phenol showed less increase in viscosity than the blends containing only the orthoalkylated phenol or the calcium sulfonate. Further, it is to be noted that blend No. 13, which contained both sulfurized nonyl barium phenate and orthoalkylated phenol, showed an increase in viscosity of 24 against an increase in viscosity of 29 for blend No. 8, which contained only the sulfurized nonyl barium phenate. It is to be noted that neither blend 8 nor blend 13 contained any of the alkaline earth sulfonate. Furthermore, comparing blend 13 with blend 14, where the mixture of calcium sulfonate and co-neutralized sulfurized nonyl calcium-barium phenate, having a ratio of 1:2, was employed, a synergistic effect was not noted. This is also evidenced by blend No. 15. On the other hand, blend N0. 10, where two parts of barium sulfonate and one part of co-neutralized sulfurized nonyl calciumbarium phenate was used, a viscosity increase of 34 was realized and when this material was used with the orthoalkylated phenol, as shown in blends 16 and 18, a synergistic eifect was noted. This effect is also shown in blends 20 and 21.

From the data presented in the table, it may be concluded that the alkaline earth metal sulfonate should be employed with the co-neutralized sulfurized alkyl phenate in a ratio of two parts of the alkaline earth metal sulfomate to one part of the phenate to obtain the synergistic effect when employed with the orthoalkylated phenol.

The Indiana Life test employed to show the beneficial effects of the present invention is described in The Journal of Industrial and Engineering Chemistry, Analytical Edition, vol. 6, page 419, by Rogers and Shoemaker. The Modified Indiana Life test consists in suspending a rod having strips of copper, iron and zinc wrapped thereon in the oil during the oxidation period and the withdrawal of samples of sufi'icient amount at specified intervals for determination of viscosity from which the viscosity increase is calculated.

The present invention is quite useful in that heavy duty lubricating oil possessing outstanding cleanliness, antiwear and stability characteristics is provided for use in lubricating internal combustion and other types of engines subjected to heavy duty. The lubricating oil composition in accordance with the present invention is quite useful when employed in lubricating engines such as those of the Chevrolet type possessing outstanding stability and cleanliness.

The nature and objects of the present invention having been completely described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is:

1. A lubricating oil composition of improved stability which consists of synergistic amounts in the range between about 0.5% and about 2.0% by weight of an orthoalkylated phenol consisting of 2,6 ditertiary butyl a dimethyl amine para-cresol, between about 1% and about 5% by weight of an alkaline earth metal sulfonate inhibitor containing a co-neutralized sulfurized nonyl phenate, said alkaline earth metal sulfonate and co-neutralized sulfurized nonyl phenate being in a ratio of about 2: 1, and between about 93% and about 98.5% by weight of a lubricating oil.

2. A composition in accordance with claim 1 in which the alkaline earth metal is calcium.

3. A composition in accordance with claim 1 in which the alkaline earth metal is barium.

References Cited in the file of this patent UNITED STATES PATENTS 2,270,577 Bergstrom et al. Jan. 20, 1942 2,410,652 Grifiin et al. Nov. 5, 1946 2,629,693 Barton et al. Feb. 24, 1953 2,652,367 Adelson Sept. 15, 1953 2,693,448 Landis et al. Nov. 2, 1954 2,695,273 Hook et al. Nov. 23, 1954 2,750,340 Gerhardt et al. June 12, 1956 FOREIGN PATENTS 497,953 Canada Nov. 24, 1953 607,013 Great Britain Aug. 24, 1948 

1. A LUBRICATING OIL COMPOSITION OF IMPROVED STABILITY WHICH CONSISTS OF SYNERGISTIC AMOUNTS IN THE RANGE BETWEEN ABOUT 0.5% AND ABOUT 2.0% BY WEIGHT OF AN ORTHOALKYLATED PHENOL CONSISTING OF 2,6 DITERTIARY BUTYL A DIMETHYL AMINE PARA-CRESOL, BETWEEN ABOUT 1% AND ABOUT 5% BY WEIGHT OF AN ALKALINE EARTH METAL SULFONATE INHIBITOR CONTAINING A CO-NEUTRALIZED SULFURIZED NONYLPHENATE, SOLID ALKALINE EARTH METAL SULFONATE AND CO-NEUTRALIZED SULFURIZED NONYL PHENATE BEING IN A RATIO OF ABOUT 2:1, AND BETWEEN ABOUT 93% AND ABOUT 98.5% BY WEIGHT OF A LUBRICATING OIL. 